TW202223056A - Resin molding for optical semiconductor sealing capable of providing an optical semiconductor sealing material with superior temperature cycle resistance - Google Patents

Abstract

The present invention provides a resin molding for optical semiconductor sealing, which provides an optical semiconductor sealing material with superior temperature cycle resistance. The resin molding for optical semiconductor sealing of the present invention includes a compound of a structural unit (I) represented by the following formula (I), and a compound of a structural unit (II) represented by the following formula (II). (In the formula, A1 represents an organic group; R1 represents an organic group having a non-aromatic ring.) (In the formula, A1 is as described above; R2a represents a site containing a residue of an epoxy resin; R2b represents a hydrogen atom or a bonding key bond with R2a.).

Description

Resin molding for optical semiconductor sealing

The present invention relates to a resin molded product for sealing an optical semiconductor.

The optical semiconductor element is encapsulated by a ceramic package or a plastic package to be deviced. Here, since the constituent materials of ceramic packages are relatively expensive and have poor mass production, the use of plastic packages has become the mainstream. Among them, from the viewpoints of workability, mass productivity, and reliability, a technique of transferring an epoxy resin composition obtained by preliminarily ingot-molding it into an ingot form has become mainstream.

Patent Document 1 discloses a technique of granulating an epoxy resin composition into a granular form and making it into an ingot. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2011-9394

[Problems to be Solved by Invention]

In recent years, with the high functionalization and high output of electronic equipment, higher reliability is required for optical semiconductors. For example, due to use in an environment where the temperature is repeatedly changed from low temperature to high temperature, cracks, peeling, or discoloration of the sealing material may occur, and it is necessary to reduce the damage to the optical semiconductor element caused by these.

The objective of this invention is to provide the resin molded object for optical semiconductor sealing which provides the optical semiconductor sealing material excellent in temperature cycle resistance. [Technical means to solve problems]

(式中，A ¹表示有機基；R ¹表示具有非芳香族環之有機基) 式(II)： [化2]

(式中，A ¹如上所述；R ^2a表示包含環氧樹脂之殘基之部位；R ^2b表示氫原子或與R ^2a鍵結之鍵結鍵) The present invention relates to a resin molded article for optical semiconductor sealing, comprising: a compound having a structural unit (I) represented by the following formula (I) and a compound having a structural unit (II) represented by the following formula (II) the compound. Formula (I): [Formula 1]

(In the formula, A ¹ represents an organic group; R ¹ represents an organic group having a non-aromatic ring) Formula (II): [Chemical 2]

(in the formula, A ¹ is as described above; R ^2a represents a site containing a residue of an epoxy resin; R ^2b represents a hydrogen atom or a bonding bond with R ^2a )

It is preferable that the said resin molded object for optical semiconductor sealing satisfy|fills the following relational expression (1). Y＜370000X－36000000 (1) (in the formula, X represents the glass transition temperature (°C) of the hardened body (size: width 5 mm×length 35 mm×thickness 1 mm) obtained by the following method, and Y represents the storage of the above hardened body at 265°C Modulus of elasticity (Pa)) (How to make a hardened body) The resin molded product was heated at 150° C. for 4 minutes to be molded, and then heated at 150° C. for 3 hours to obtain a hardened body.

The molar ratio of the structural unit (I) to the total of the structural unit (I) and the structural unit (II) is preferably 0.10 to 0.60.

It is preferable that the above-mentioned resin molding for optical semiconductor sealing has a linear transmittance of 70 at a wavelength of 450 nm when it is made into a hardened body (size: width 50 mm × length 50 mm × thickness 1 mm) by the following method. %above. (How to make a hardened body) The resin molded product was heated at 150° C. for 4 minutes to be molded, and then heated at 150° C. for 3 hours to obtain a hardened body.

The present invention also relates to an optical-semiconductor sealing material obtained by molding the above-mentioned resin molding for optical-semiconductor sealing.

The present invention also relates to an optical semiconductor device including: an optical semiconductor element; and the above-mentioned optical semiconductor sealing material that seals the optical semiconductor element. [Effect of invention]

According to the resin molded product for optical semiconductor sealing of the present invention, since an optical semiconductor sealing material excellent in temperature cycle resistance can be obtained, even if it is used in an environment where the temperature repeatedly changes from low temperature to high temperature, the optical semiconductor sealing material is not easily generated. Cracks, peeling, or discoloration, etc., can reduce the damage to the optical semiconductor element caused by these.

Hereinafter, the present invention will be specifically described.

(式中，A ¹表示有機基；R ¹表示具有非芳香族環之有機基) [化4]

(式中，A ¹如上所述；R ^2a表示包含環氧樹脂之殘基之部位；R ^2b表示氫原子或與R ^2a鍵結之鍵結鍵) The resin molding for optical semiconductor sealing of this invention contains the compound which has the structural unit (I) represented by following formula (I), and the compound which has the structural unit (II) represented by following formula (II). [hua 3]

(In the formula, A ¹ represents an organic group; R ¹ represents an organic group having a non-aromatic ring) [Chem. 4]

(in the formula, A ¹ is as described above; R ^2a represents a site containing a residue of an epoxy resin; R ^2b represents a hydrogen atom or a bonding bond with R ^2a )

Since the resin molded product for optical semiconductor sealing of the present invention contains the compound having the structural unit (I), it provides a hardened body with a high glass transition temperature and a low elastic modulus at high temperature, so that temperature cycle resistance can be obtained. Excellent optical semiconductor sealing material. Furthermore, the photosemiconductor sealing material which is excellent also in reflow resistance, yellowing resistance, dimensional stability with respect to a temperature change, impact absorption, and impact resistance can be obtained. Such a photosemiconductor sealing material is less prone to cracks, peeling, or discoloration even when used in a high-temperature environment or during a reflow process, so that damage to the photosemiconductor element caused by these can be reduced.

Generally, when the glass transition temperature rises, the elastic modulus also tends to rise, but the elastic modulus with a higher glass transition temperature and a higher temperature side than the glass transition temperature can be obtained from a resin molded product containing a compound having the structural unit (I). Lower hardened body. The reason for this is not clear, but it is presumed that because the steric repulsion of the molecular chain represented by R ¹ is large, the rigidity of the main chain of the above-mentioned compound increases, the glass transition temperature rises, and the free volume of the above-mentioned compound increases, elasticity. Modulus is reduced.

Moreover, since the resin molded object for optical semiconductor sealing of this invention does not become too hard at the time of thermoforming, it is excellent in handleability, moldability, and mold release property.

In formula (I), A ¹ represents an organic group. The above-mentioned organic group is a divalent organic group. The number of carbon atoms in the organic group is preferably 2 or more, more preferably 6 or more, more preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. The organic group is preferably a hydrocarbon group, and may contain a heteroatom such as an oxygen atom or an unsaturated bond such as a double bond. The above-mentioned organic group may have a ring structure, and preferably has a ring structure.

In formula (I), R ¹ represents an organic group having a non-aromatic ring. The above-mentioned organic group represents a divalent organic group. The number of carbon atoms in the organic group is preferably 3 or more, more preferably 5 or more, still more preferably 6 or more, and more preferably 30 or less, more preferably 20 or less. The organic group is preferably a hydrocarbon group, and may contain a heteroatom such as an oxygen atom or an unsaturated bond such as a double bond.

The above-mentioned non-aromatic ring is more preferably a non-aromatic carbocyclic ring. The above-mentioned non-aromatic ring may have an unsaturated bond, but it is also preferable not to have an unsaturated bond. The above-mentioned non-aromatic ring may be monocyclic or polycyclic.

The above-mentioned non-aromatic ring may also be a hydrocarbon ring having a bridged structure. As the hydrocarbon ring having a bridge structure, a bicyclic or tricyclic hydrocarbon ring having a bridge structure is preferable, and a tricyclic hydrocarbon ring having a bridge structure is more preferable.

As said non-aromatic ring, a cyclohexane ring is especially preferable.

R ¹ may be a group obtained by removing two hydroxyl groups from a polyol having a non-aromatic ring described later.

In formula (II), R ^2a represents a site containing a residue of an epoxy resin. In this specification, the residue of the epoxy resin is a structure obtained by removing at least one epoxy group (ethylene oxide ring) from the epoxy resin. R ^2a may further include one or more unreacted epoxy groups, and may further include a structure in which an epoxy group reacts with other compounds (hardeners, hardening accelerators, other additives, etc.).

In formula (II), R ^2b represents a hydrogen atom or a bonding bond to R ^2a . When R ^2b is a bonding bond, it bonds with R ^2a to form a ring.

In the resin molded product for optical semiconductor sealing of the present invention, the molar ratio (I/(I+II)) of the structural unit (I) to the total of the structural unit (I) and the structural unit (II) is preferably 0.10 to 0.60 . The above-mentioned molar ratio is more preferably 0.15 or more, more preferably 0.25 or more, and more preferably 0.50 or less, and still more preferably 0.40 or less. Thereby, the photosemiconductor sealing material which is more excellent in temperature cycle resistance and reflow resistance can be obtained. The content of each structural unit can be determined by NMR (Nuclear Magnetic Resonance, nuclear magnetic resonance).

It is preferable that the resin molded object for optical semiconductor sealing of this invention satisfy|fills the following relational expression (1). Y＜370000X－36000000 (1) (in the formula, X represents the glass transition temperature (°C) of the hardened body (size: width 5 mm×length 35 mm×thickness 1 mm) obtained by the following method, and Y represents the storage of the above hardened body at 265°C Modulus of elasticity (Pa)) (How to make a hardened body) The resin molded product was heated at 150° C. for 4 minutes to be molded, and then heated at 150° C. for 3 hours to obtain a hardened body. When such a resin molding is hardened, a hardened body having a higher glass transition temperature and a lower elastic modulus at a high temperature can be obtained, so that a photosemiconductor sealing material with more excellent temperature cycle resistance can be obtained.

Regarding the glass transition temperature (Tg), the dynamic viscoelasticity measurement (mode: stretching, scanning temperature: 0 to 270°C, frequency: 1 Hz, heating rate: 10°C/min, distance between sample supports: 22.5 mm), obtain storage elastic modulus E' and loss elastic modulus E'', and obtain tanδ (=E ''/E') curve, and the peak top temperature of tanδ was obtained as the glass transition temperature (Tg).

The above-mentioned storage elastic modulus (E' _{265 ℃} ) at 265 ℃ was obtained by using the hardened body (size: width 5 mm × length 35 mm × thickness 1 mm) obtained by the above method, and the dynamic Viscoelasticity measurement (mode: stretching, scanning temperature: 0 to 270° C., frequency: 1 Hz, heating rate: 10° C./min, distance between sample supports: 22.5 mm) was obtained.

It is preferable that the glass transition temperature (Tg) of the resin molded product for optical semiconductor sealing of the present invention is 110° C. or higher when it is made into a cured body (size: width 5 mm×length 35 mm×thickness 1 mm) by the above-mentioned method , more preferably 120°C or higher, still more preferably 130°C or higher, particularly preferably 140°C or higher, and more preferably 200°C or lower. When Tg when it becomes a hardened body is in the said range, the photosemiconductor sealing material which is more excellent in temperature cycle resistance can be obtained.

The storage elastic modulus at 265°C (E' ₂₆₅ ) of the resin molded product for encapsulating an optical semiconductor of the present invention in the case of a cured body (size: width 5 mm × length 35 mm × thickness 1 mm) by the above-mentioned method _°C ) is preferably 5.0×10 ⁷ Pa or less, more preferably 2.0×10 ⁷ Pa or less, still more preferably 1.0×10 ⁷ Pa or less, and more preferably 1.0×10 ⁶ Pa or more. When E' _{265 °C} in the case of a hardened body is within the above-mentioned range, a photosemiconductor sealing material which is more excellent in temperature cycle resistance and reflow resistance can be obtained.

The storage elastic modulus (E' ₂₅ ) at 25°C of the resin molded product for optical semiconductor encapsulation of the present invention when it is made into a hardened body (size: width 5 mm x length 35 mm x thickness 1 mm) by the above method _°C ) is preferably 5.0×10 ⁸ to 5.0×10 ⁹ Pa, more preferably 8.0×10 ⁸ to 4.0×10 ⁹ Pa, still more preferably 1.0×10 ⁹ to 3.0×10 ⁹ Pa. When E' _{25 °C} in the case of a hardened body is within the above-mentioned range, a photosemiconductor sealing material which is more excellent in temperature cycle resistance and reflow resistance can be obtained.

E' _{25 °C} was measured by dynamic viscoelasticity at 25°C (mode: stretching, scanning temperature: 0 to 270°C, frequency: 1 Hz, heating rate: 10°C/min, distance between sample supports: 22.5 mm).

When the resin molded product for optical semiconductor sealing of the present invention is formed into a cured body (size: width 50 mm x length 50 mm x thickness 1 mm) by the above method, the linear transmittance at a wavelength of 450 nm is preferably 70 % or more, more preferably 90% or more, still more preferably 95% or more. Thereby, the optical semiconductor sealing material excellent in translucency (transparency) can be obtained. The said linear transmittance was calculated|required by measuring the transmission spectrum in wavelength 450 nm of the said hardened body using a spectrophotometer.

It is preferable that the resin molding for optical semiconductor sealing of this invention contains epoxy resin, acid anhydride, polyhydric alcohol, the reactant of epoxy resin and acid anhydride, the reactant of polyhydric alcohol and acid anhydride, and a hardening accelerator. The compound having the above-mentioned structural unit (I) may be a reactant of a polyol and an acid anhydride, and the compound having the structural unit (II) may be a reactant of an epoxy resin and an acid anhydride.

As epoxy resins, those with less coloration are preferred, and examples thereof include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins, isocyclic epoxy resins, etc. Heterocyclic epoxy resins such as triglycidyl cyanurate, hydantoin epoxy resins, hydrogenated bisphenol A epoxy resins, aliphatic epoxy resins, glycidyl ether epoxy resins, etc. The epoxy resins may be used alone or in combination of two or more.

As the acid anhydride, for example, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic dianhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, Tetrahydrophthalic anhydride, methyl resistant anhydride, resistant anhydride, glutaric anhydride, etc. The acid anhydride may be used alone or in combination of two or more.

Although the compounding quantity of an acid anhydride is not specifically limited, For example, 20-200 mass parts is preferable with respect to 100 mass parts of epoxy resins. If it is less than 20 parts by mass, the rate of hardening will be slow, and if it exceeds 200 parts by mass, it will be present in excess for the hardening reaction, so there is a possibility that various physical properties may be lowered.

Furthermore, the equivalent ratio (A/E) of the equivalent weight (A) of the acid anhydride group and the equivalent weight (E) of the epoxy group is preferably 0.5 to 1.5, more preferably 0.8 to 1.2, and most preferably 0.9 to 1.0. If it is less than 0.5 or exceeds 1.5, the reactivity decreases, and the strength and heat resistance of the cured product may be impaired.

The polyol may be a compound having two or more hydroxyl groups, preferably a glycol.

As the above-mentioned polyol, a polyol having a non-aromatic ring is preferable because the above-mentioned structural unit (I) can be easily obtained. The above-mentioned polyol may also be an alicyclic polyol. The carbon number of the above-mentioned polyol is preferably 3 or more, more preferably 5 or more, still more preferably 6 or more, and more preferably 30 or less, more preferably 20 or less.

As said non-aromatic ring, the non-aromatic ring similar to the non-aromatic ring which the organic group which is R< ¹ > in said formula (I) has is mentioned.

As said polyol, the following polyols can be illustrated, but it is not limited to these. Furthermore, where stereoisomers exist, each stereoisomer and a mixture of two stereoisomers are also included in the examples. [hua 5]

The polyols may be used alone or in combination of two or more.

The compounding quantity of a polyhydric alcohol is not specifically limited, For example, it can select suitably from the range of 5-200 mass parts with respect to 100 mass parts of epoxy resins. Further, the molar ratio (B/C) of the molar number (B) of the polyol compound and the molar number (C) of the acid anhydride is preferably 0.01 to 0.70, more preferably 0.05 to 0.60, and most preferably 0.10 to 0.50 . If the compounding amount of the polyol is too small, the elastic modulus of the obtained hardened body may be too high. On the other hand, if the compounding amount of the polyol is too large, the glass transition temperature and the elastic modulus of the obtained hardened body may be increased. Sometimes too low.

Examples of the curing accelerator include: tertiary amines such as triethanolamine and dimethylbenzylamine; imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole; tetraphenylphosphonium tetraphenylborate , triphenylphosphine and other organophosphorus compounds; 1,8-diazabicyclo[5.4.0]undecene-7, 1,5-diazabicyclo[4.3.0]nonene-5 and other diaz Bicyclic olefin-based compounds, etc. These can be used individually or in combination of 2 or more types similarly.

The compounding quantity of a hardening accelerator is not specifically limited, For example, it can select suitably from the range of 0.1-5 mass parts with respect to 100 mass parts of epoxy resins, Preferably it is 0.5-3 mass parts, More preferably, it is 1-2 mass parts. If the compounding amount of the hardening accelerator is too small, the rate of hardening may become slow and productivity may decrease. On the other hand, if the compounding amount of the hardening accelerator is too large, the rate of the hardening reaction may be accelerated, and it may be difficult to control the reaction state, resulting in The risk of uneven response.

When the resin molding for optical semiconductor sealing of this invention contains a hardening accelerator, a part of hardening accelerator may react with an epoxy resin and/or an acid anhydride.

In the resin molding for optical semiconductor encapsulation of the present invention, in addition to the above components, an anti-coloring agent, a lubricant, a modifier, an anti-deterioration agent, a mold release agent, a phosphor for changing the wavelength of light, or Additives such as inorganic and organic fillers that diffuse light. Furthermore, as long as the transmission of light is not impaired, a filler such as silica powder can be mixed.

As an anti-coloring agent, a phenol type compound, an amine type compound, an organic sulfur type compound, a phosphine type compound, etc. are mentioned.

As the lubricant, waxes such as stearic acid, magnesium stearate, and calcium stearate, and talc may, for example, be mentioned. In addition, in the case of mixing the above-mentioned lubricant, the mixing amount is appropriately set according to the molding conditions, for example, it is preferably set to 0.1 to 0.4 mass % of the entire resin molding.

Examples of phosphors that change the wavelength of light and inorganic and organic fillers that diffuse light include silica powders such as silica glass powder, talc, fused silica powder, and crystalline silica powder, alumina, Silicon nitride, aluminum nitride, silicon carbide, etc. Furthermore, in the case of mixing phosphors or inorganic and organic fillers, the mixing amount is appropriately set according to molding conditions. Specifically, in the case of a phosphor, the compounding amount of the phosphor can be appropriately set in the range of 1% by mass to 60% by mass of the entire resin molded product. On the other hand, in the case of the light-scattering filler (organic, inorganic), the light-scattering filler can be appropriately set from 0.5 mass % to 25 mass % of the entire resin molded product.

As a resin molded object for optical semiconductor sealing of this invention, an ingot, a sheet, etc. are mentioned.

When the resin molding for optical semiconductor sealing is an ingot, the volume is not particularly limited, but is preferably 1 to 100 cm ³ , more preferably 10 to 100 cm ³ .

Since the resin molding for optical semiconductor sealing of this invention is used for resin sealing of optical semiconductor elements, such as a light-receiving element, it is preferable to be transparent from an optical viewpoint. Here, "transparent" means that the transmittance at 400 nm of the hardened body of the above-mentioned molded product is 90% or more. Furthermore, when the above-mentioned additives such as phosphors that change the wavelength of light or inorganic and organic fillers that diffuse light are contained, the transmittance refers to the transmittance of the resin portion after removing the additives.

The resin molding for optical semiconductor sealing of the present invention can be suitably produced, for example, by the following production method including the following steps: The step of kneading epoxy resin, acid anhydride, polyol, and hardening accelerator to obtain a curable resin composition; the step of heat-treating the curable resin composition; the step of granulating the curable resin composition to obtain a granular curable resin composition; and A step of molding the granular curable resin composition.

The method of kneading is not particularly limited, and for example, a method using an extruder can be mentioned. The kneading temperature is also not particularly limited, and can be appropriately changed according to the properties of the epoxy resin.

The shape of the curable resin composition obtained by kneading is not particularly limited, and examples thereof include a film shape, a sheet shape, a granular shape, and a block shape.

The curable resin composition obtained by kneading was heat-treated to obtain a B-stage (semi-cured) optical semiconductor sealing resin composition. The heat treatment temperature and heat treatment time are not particularly limited, and can be appropriately changed according to the properties of the epoxy resin.

The heat-treated resin composition is pelletized to obtain a pelletized curable resin composition. It can also be pulverized using a ball mill, a turbo pulverizer, or the like before granulation. The granulation method is not particularly limited, and examples thereof include a method using a dry compression granulator. The average particle diameter of the granular material obtained by granulation is not particularly limited, but is preferably 1 to 5000 μm, more preferably 100 to 2000 μm. If it exceeds 5000 μm, the compressibility tends to decrease.

The obtained granular curable resin composition is molded to obtain a molded product. As the molded product, an ingot or a sheet may be mentioned, and as a molding method, ingot molding to obtain an ingot, or extrusion molding to obtain a sheet may, for example, be mentioned. Since the obtained molded product can provide a hardened body with a high glass transition temperature and a low elastic modulus as described above, it is possible to provide a photosemiconductor sealing material excellent in heat resistance and reflow resistance.

When the molded product is an ingot, the conditions for ingot molding into an ingot are appropriately adjusted according to the composition, average particle size, or particle size distribution of the granular curable resin composition. Usually, the compression ratio during ingot molding is used. It should be set to 90% to 96%. That is, the reason is that if the value of the compression ratio is less than 90%, the density of the ingot will decrease, and there is a possibility of easy cracking; on the contrary, if the value of the compression ratio is more than 96%, cracks will be generated during ingot casting and the mold will be released. There is a risk of chipping or breaking.

The resin molding for optical semiconductor sealing of this invention can seal an optical semiconductor element by molding methods, such as transfer molding. The optical semiconductor sealing material obtained by shaping|molding the resin molded object for optical semiconductor sealing of this invention is also one of this invention. Since the optical semiconductor sealing material of this invention is obtained from the resin molded object of this invention, it is excellent in temperature cycle resistance. Furthermore, it is excellent in reflow resistance, yellowing resistance, dimensional stability against temperature change, shock absorption, and impact resistance. Therefore, even due to use in an environment where the temperature is repeatedly changed from low temperature to high temperature or due to the reflow process, there are fewer cracks or peeling, thereby reducing damage to the sealed photo-semiconductor element. In this specification, an optical-semiconductor sealing material is formed so that the optical-semiconductor element which comprises an optical-semiconductor device may be covered, and the member which seals this element.

An optical-semiconductor device provided with the optical-semiconductor element and the optical-semiconductor sealing material of this invention which seals this optical-semiconductor element is also one of this invention. Since the optical-semiconductor device of the present invention includes the optical-semiconductor sealing material of the present invention, even when operating in an environment where the temperature is repeatedly changed from low temperature to high temperature, cracks and peeling of the sealing material are less, and the optical-semiconductor element is less susceptible to cracking or peeling. less damage.

The resin molded product for optical semiconductor sealing of the present invention is particularly suitable for sealing of automotive optical semiconductors, which are used in environments where the temperature is repeatedly changed from low temperature to high temperature in many cases, and are often used in the reflow process. [Example]

Next, although an Example is given and this invention is demonstrated in detail, this invention is not limited only to these Examples.

The materials used are shown below. Epoxy resin A: Bisphenol A epoxy resin (JER-1002W manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 650) Epoxy resin B: Triglycidyl isocyanurate (TEPIC-S manufactured by Nissan Chemical Co., Ltd., epoxy equivalent: 100) Acid anhydride: Hexahydrophthalic anhydride (Rikacid HH, manufactured by Nippon Chemical Co., Ltd.) Diol Additive A: 1,4-Cyclohexanedimethanol Diol Additive B: 1,4-cyclohexanediol Diol Additive C: Hydrogenated Bisphenol A Diol Additive D: 1,6-Hexanediol Glycol Additive E: Neopentyl Glycol Hardening accelerator: dimethylbenzylamine

Examples 1 to 6 and Comparative Examples 1 to 4 Each component shown in Table 1 was melt-mixed at 50-140 degreeC in the ratio shown in this table, and it cooled, and obtained the epoxy resin composition. The obtained epoxy resin composition was subjected to reactivity adjustment at 40 to 80° C., pulverized, and ingot-molded to produce a resin ingot for optical semiconductor encapsulation.

Using the ingots produced in the respective Examples and Comparative Examples, various physical properties were measured by the methods shown below, and temperature cycle resistance, reflow resistance, and transparency were evaluated. The results are shown in Table 1.

＜Mole ratio of structural unit＞ The content of the structural unit A derived from the reaction product of the diol additive and the acid anhydride and the content of the structural unit B derived from the reaction product of the epoxy resin and the acid anhydride were determined by NMR, and the structural unit A relative to the structural unit A and the structural unit B were calculated. The total molar ratio (A/(A+B)).

<Production of test piece (hardened body)> Using the ingot produced as described above, it was molded with a dedicated mold (hardening condition: heating at 150° C.×4 minutes) to produce a hardened product for a test piece having a size corresponding to the measurement method. By heating this at 150 degreeC for 3 hours, hardening was complete|finished completely, and the test piece was obtained.

<Storage elastic modulus E'> Using the above-produced test piece (size: width 5 mm × length 35 mm × thickness 1 mm), with RSA-II manufactured by RHEOMETRIC SCIENTIFIC company, in tensile mode, frequency 1 Hz, scanning temperature 0 ~ 270 ℃, heating Under the measurement conditions of a speed of 10°C/min and a distance between the sample supports of 22.5 mm, the storage elastic modulus E' of the test piece was obtained, and the storage elastic modulus of the hardened body at a measurement temperature of 265°C was derived.

<Glass transition temperature (Tg)> Using RSA-II manufactured by RHEOMETRIC SCIENTIFIC, under the measurement conditions of stretching mode, frequency 1 Hz, scanning temperature 0-270°C, heating rate 10°C/min, and distance between sample support points 22.5 mm, the above fabricated sample was obtained. The storage elastic modulus E' and the loss elastic modulus E'' of the test piece (size: width 5 mm × length 35 mm × thickness 1 mm), according to which the curve of tanδ (=E''/E') is obtained , and the peak top temperature of tanδ was obtained as the glass transition temperature. Moreover, the value of 370000X-36000000 when glass transition temperature is made into X was also calculated|required.

<Linear transmittance> First, a quartz tank was filled with liquid paraffin manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., and a reference line was measured using a spectrophotometer V-670 manufactured by Japan Spectrophotometer. Then, the test piece (size: width 50 mm × length 50 mm × thickness 1 mm) prepared above was immersed in liquid paraffin in a quartz tank, and the light transmittance at a wavelength of 450 nm was measured. In addition, evaluation was performed based on the following criteria. ○: Linear transmittance of 70% or more ×: Linear transmittance less than 70%

＜Production of Evaluation Package＞ As shown in Fig. 1, the ingot produced above was used so as to cover the end of the reliability evaluation frame (Ag) manufactured by Hirai Precision Industry Co., Ltd., and formed into a size: width 5 mm × length 6 mm × thickness 2 mm (hardened Conditions: heating at 150°C x 4 minutes). By heating it at 150°C for 3 hours to complete the hardening, an evaluation package was obtained. For each Example and Comparative Example, 20 packages described above were produced.

<Temperature cycle test (TCT)> The above packages were exposed to high temperature (130°C) and low temperature (-40°C) for 15 minutes each. Complete recovery to each temperature within 5 minutes. Using this as a cycle, a temperature cycling test of 1000 cycles was performed on the above package. After that, the packages were taken out, the presence or absence of cracks was observed, and the number of packages with cracks among 20 packages was counted and evaluated according to the following criteria. ○: 0 to 5 △: 6 to 10 ×: 11 or more

＜Reflow soldering＞ The above package was passed through a reflow oven three times (265°C x 10 seconds at peak).

<Reflow Soldering Resistance> The package subjected to the above-mentioned reflow soldering was immersed in red ink manufactured by Taiyo Co., Ltd. and decompressed for 10 minutes. After that, the package was taken out, and the infiltration of the ink was visually observed. The number of packages with poor peeling among 20 packages was counted, and the reflow resistance was evaluated according to the following criteria. ○: 0 to 5 ×: 6 or more

[Table 1] Example serial number Example Comparative example 1 2 3 4 5 6 1 2 3 4 Composition (parts by mass) Epoxy A 60 60 60 60 60 60 60 60 60 60 epoxy resin B 40 40 40 40 40 40 40 40 40 40 anhydride 75 75 75 75 75 75 75 75 75 75 Diol Additive A 12.9 22.2 Diol Additive B 10.4 17.9 Glycol Additive C 21.4 37 Glycol Additive D 10.6 18 Glycol Additive E 9.2 16 hardening accelerator 1 1 1 1 1 1 1 1 1 1 A/(A＋B) 0.20 0.20 0.20 0.34 0.34 0.34 0.20 0.20 0.34 0.34 E'(×10 ⁶ Pa)(Y) at 265℃ 10.8 14.0 13.2 8.3 8.2 8.3 13.1 14.2 7.9 8.0 Tg(℃)(X) 148.0 152.1 153.9 125.2 134.1 143.6 129.5 135.3 110.0 118.7 370000X－36000000(×10 ⁶ ) 18.8 20.3 20.9 10.3 13.6 17.1 11.9 14.1 4.7 7.9 450 nm linear transmittance (%) 97.6 97.4 97.9 97.5 98.6 97.9 98.0 98.2 97.5 98.3 TCT durability evaluation ○ ○ ○ △ △ ○ △ △ × × Evaluation of reflow resistance × × × ○ ○ ○ × × ○ ○ Transparency Evaluation ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ [Industrial Availability]

The present invention relates to an optical semiconductor sealing resin molding, an optical semiconductor sealing material, and an optical semiconductor device for sealing an optical semiconductor element, which can be used for manufacturing the optical semiconductor device.

FIG. 1 is a schematic diagram showing evaluation packages used in Examples and Comparative Examples.

Claims (6)

A resin molded article for optical semiconductor sealing, comprising: a compound having a structural unit (I) represented by the following formula (I) and a compound having a structural unit (II) represented by the following formula (II), (I): [Chemical 1]

(In the formula, A ¹ represents an organic group; R ¹ represents an organic group having a non-aromatic ring) Formula (II): [Chemical 2]

(In the formula, A ¹ is as described above; R ^2a represents a site containing a residue of an epoxy resin; R ^2b represents a hydrogen atom or a bond to which R ^2a is bonded). As claimed in claim 1, the optical semiconductor sealing resin molded article satisfies the following relational expression (1): Y＜370000X－36000000 (1) (in the formula, X represents the glass transition temperature (°C) of the hardened body (size: width 5 mm×length 35 mm×thickness 1 mm) obtained by the following method, and Y represents the storage of the above hardened body at 265°C Modulus of elasticity (Pa)) (How to make a hardened body) The resin molded product was heated at 150° C. for 4 minutes to be molded, and then heated at 150° C. for 3 hours to obtain a hardened body. The resin molding for optical semiconductor sealing according to claim 1 or 2, wherein the molar ratio of the structural unit (I) to the total of the structural unit (I) and the structural unit (II) is 0.10 to 0.60. The resin molded article for optical semiconductor sealing according to any one of claims 1 to 3, which is produced at a wavelength of The linear transmittance at 450 nm is more than 70%, (How to make a hardened body) The resin molded product was heated at 150° C. for 4 minutes to be molded, and then heated at 150° C. for 3 hours to obtain a hardened body. An optical-semiconductor sealing material obtained by shaping|molding the resin molded object for optical-semiconductor sealing in any one of Claims 1-4. An optical semiconductor device comprising: an optical semiconductor element; and the optical semiconductor sealing material according to claim 5, which seals the optical semiconductor element.

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